Process for the production of amylose films



ci 45a Patented Sept. 2, 1952 UNITED STATES PATENT OFFICE PROCESS FOR THE PRODUCTION or AMYLOSE FILMS Ivan A. Wolff, Howard'A. Davis, James E. Cluskey,

and Laetta J. Gundrum, Peoria, Ill., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Application August 1,1950,

. Serial .No. 177,114

16 Claims; (CI. 18-57) 22, 1949, by Davis et al., there is described-a method for producing amylaceous films consisting'predominately of amylose, the linear fraction of starch. In that application amylose or starch composed predominately .of. amylose is dissolved in an aqueous solution'containing an amylose-complexing agent, such as low'molecular' weight aliphatic alcohols, such as ethanoL'pr'o-qo panol; butanol, pentanol and the like, low molec-' ular weight glycol ether'sii. e. glycol rethers of low molecular weight alcohols); such as diethyl Cellosolv, organic bases,'such as pyridine or other agencies as disclosed, for example by Whistler and Hilbertin JACS 6'7, 1161 (1943). Forthe purpose of their invention, Davis et al. employ those :amylo'se-complexing agents having appreciable solubility in water.' j

An amylosecomplexingagent is a reagent which selectively precipitates amylose from starch paste by combining withthe amylose in. the "form .of a'molecular complex. Starchhas, beenfractionated by suspending; it in an aqueous 7 medium in the presence of .a wide variety. of; chemical agents known as complexing, agents. The suspension is then heated-andaftertheQ solution is complete, it is cooled slowlygwhere upon the amylose precipitates in the form of a; complex'jwith the complexing agent. The precip- 40 itatedlcoinplex may be separated, thus effect-f. ing a separation between amylose and ainylo}; pectin. Complexing agents for amylose constitute a class of reagents well-known and ,e stablishedlin carbohydrate chemistry. Although the compl ingiagentsas'sisjt in separating amylose from a mixture with amylopectin, by precipitatioiiupo'nf cooling, wehave found that'they also servejfto' promote solution of amyloseupon heating.

For the sake of brevity the term amylose films 5 as used hereinafter is intended to refer to film's composed predominatelyi'of amylose! The term "amylose ias usedinthis specificationire'fers to'a polydispe'rse, predominately. linear .lji-linked anhydroglucose polymer usually obtained by the 5 I amended April 30, 1928; 370- 0. G. 757) of March 3, 1883, as

fractionation of starch. This starch fraction is also known as the A fraction.

In preparing their amylose film-forming solutions the inventors prefer to wet the amylose with thecomplexing compound, adding the wet powder or slurry to hot water, with vigorous agitation. The solutions may also be prepared by saturating the water with the complexing compound and then adding the powdered amylose. The specific manner in which the solution is finally obtained is not critical, however, since it is only necessary that a relatively clear solution be obtained to produce satisfactory film.

According to the prior invention, the films wereformed by casting or spraying the solution upon' a smooth surface. The inventors found it nec-' essary in most cases to keep the'cast solution at a temperature sufiiciently high to avoidgelling' have found, for'example, that the butanol or other complexing agents as used by Davis et al.

may be removed from the casting solution as by azeotropic distillation before the solution is cast or the films are otherwise formed. We'have discoveredthe remarkable fact that films cast from such solutions are markedly superior in appearance to films cast from solutions which have contained no complexing agent and definitely superior to films cast by the Davis et al. process in which the comple'xing agent is not removed. We have discovered, moreover, that it is unnecessary in our'process to maintain the'cast films at elevated temperatures above the temperature. of gelation, in order to produce films of desired strength, transparency, and uniformity. If films made according to the prior process were permitted to cool to the point of gelation before substantially dry, the films were hazy and tended" to crack.

Moreover, the presence of small amounts of complexing reagent in the prior films often caused uneven gelation of the film result ing in a haze pattern of alternate clear'f'and cloudy areas. On the contrary, films made by our present process may becast upon plates at room temperature, allowed; to gel, and then dried These final'films are superior in clarity, smoothness and uniformity of thickness to "those obtained by theprocess at room temperature.

of :Davis 'et al. 1

Although amylose has been considered by some chemists to be completely soluble in boiling water, we have found that solutions made with water only produce poor films. The films arehazy and have a granular appearance apparently due to the presence of undissolved gel particles. The presence of undissolved gel particles may in part account for the marked inferiority of such amylose films compared with those of our. inven.-. tion, but we do not wish to be limited by an thee oretical considerations. We are unable. to explain With complete exactness.thesuperiorityrof our films.

According to our process, the amylose- .or amylaceous material composed predominantly of amylose is dissolved as previously 'describedfiwith the aid of a complexing agent. The amount-of "used for the film treatment, but this is efiective complexing agent and particular manner; in-

which the solution is obtained is not critical, and

for best results we employ afinalaqueousme-- dium approximately saturated with the complexing agent. The solution may also contain fillers, dyes, modifiers; such as.plasticizers, anditha like- After a clear solutionxis "obtained, whichemay.

require heating-nearly.:up;to;the;boiling. point, the complexing. agent is removed"as..by.ageotropic distillationt Additional..distilledrwater. may be used I initially orraddedcfor thepurpcseof obtaining.

In our researches; wee-have discovered; moreover; that amylosefilinsrar'e peculiar irrtheirstrip-- pinggproperties, and :thesepeculiaritiespften :renderjdifficult theproductiorrrofifilms: E01: exam: ple amylose films; adhere :tightly to; glass; surfaces. Although they may; be cast upon ismooth metal surfaces, particularly chrome-platedh urfacesand. stripped therefrom; the, humidity conditions at the time of ;casting, the cleanness of the surface, slight ascratchesguponithe: surface,

and other less tangible Z factors, 1 cause. the: dried film to stick unpredictably.

We have discovered that smoothlsurfaces; such.

as glass or metal; surfaces-,1; may: be prepared so.

as,-to-.render cast amyloseufilmsgreadily strippablei;

therefrom; We; treat the; surfaces; so; as .to arenader them: slightly, hydrophobic: by ruse of :,ae'ntS';=.

such: as polymeric; siliconcontaining;-substances;. The treatment maybe eiiectedwith a liquid mixture'containing unhydrolyaed ehlorosilanes. "We

after casting. The treatment is effective if applied to freshly cast film which has just gelled and. may also be applied with consonant improvement to the dried film. v

Our film improvement treatment comprises applying temperatures of the order of 120 0., i. e., Within the range of 80 to 150 C. for a period of 5ito 20iminutes. The temperature is preferably applied in the presence of steam. Saturated steamat 15 pounds p. s. i. gage pressure has been found-convenient in the laboratory for this treatment; but a'co-nsiderable range of temperature is eifective-aspreviously noted. Specific illustrations of this film treatment are embodied in Examples-9 and-10'which follow. Dry heat may be only ifiapplied soon after casting the film while it is in a gelled but not dry condition. This procedure isjembodied in Example 8.

The following specific examples illustrate the invention. Examples l-7 illustrate the removal of the complexing agent "as itswater azeotrope prior to castingthe films. Examples 2, 3, 4, and 5 also illustrate the improved: casting technique. in-..

volvingthe a use of treated castingsurfaces. Ex

amples 8 and'9 illustrate the improved. film treat? ing-method as applied to the improved. film-form'- ingprocess of this invention. ExamplelO illustrates'the wide application of our ;improved .film:

treatingprocess as applied to. amylase films in general; Examples'll and 12. are: comparative examples of films cast from an aqueousamylose. dispersion in the preparation of which" no complexing:agent wasused.

The reported haze values were determined by ASI'M test method. D'i-672-45T, "Haze.;of Transshave, nevertheless, obtained satisfactory: results j merely; by applying. preformed-silicone polymers; dissolved in ."organicsolvents.- The iproperties o i the-films araunalfected by thepresencesoffthe':

small. amounts ofstripping agent that. may-be; removed from the sui faeawith the: film-.- Prac tioalworking; limits; for Dow. Corning D.G' 200,;-

Silicone havebeenfromabout. 0.1. mg;- to -1l0.mg;.-

pen-sq. ft. on-glass-ancl from.-O-.05 to"0.5 mg. per-- sq. ft; on chromesurfaces; applied asaazflfil percent solutionin C614 and grubbeddown--thoroughly. Typical applicationsare-Ol25arm/ft? on glas We have discovered:funthermorerthat;amylose films produced. byourl process: orx'by'xthez process" ofv-thea-applicatiom for. patent: previously. men-.- tion'ed nayrbe further. improved:in';tiansparency;' water-absorption properties;.z wet strength; and fold endurance by a particular heatiztrea-tment tetrachloride:varying-5in?concentrations fromrsi parent Plasticsby Photoelectric Cell. Itshould" be notedi-that.thephysicaltests reported arenfor thefilms containingmo added plastlcizer, and. thatithis'fact 'shouldJbe borne in mind income paring. our. films with other; known: prepared: films such as cellophane or. cellulose .actate sheet- 1 ing: Thetensile strengthswere determined on: a Scott::IP--2 incline plane. Serigraph: usingrxtest strips 5 -10 mm. wide and .a': separation. between. 'jaW S of-f lllmm.

EXAMPLE? 1' A solution ofcorn amylose (93 percent amylose W and 7 percent amylopectin) was. prepare'dby adding 25 g. 130.250" ml. of water at -8550; containing 37 ml. butanoland 0.125 g. of Du. Pont Pontacyl FastBlue conc. percent. dye. The mixture. was refiuxedwith stirring.for, 10 minutes afterwhich water-butanol'azeotrope' was distilled until the distillate had 'only one.

' phase. Waterlost by distillation was replaced by.

hotwater so that the final amylose concentration...

was approximately 10 percent. The solution wasfiltered'hot 'through'a fritted glass disc to free it from* foreign matter, then cast while hot on chrome-plated surfaces which were at room tem-' perature, using a doctor blade set 0.030 inch above the plate surface. The film soon. formed an opaquegel which cleared on drying'at room temperature to 1 a transparent. clear ,blue Ifilm of ip leasingappearance. This film had... 9'p er;

centhazejandgfa. dry tensile. strength..of 16.5j

kgJmmEf at .50. percent relative humidity and.

EXAMPLE;.3..

Glass platesr l'0.'..' x: 181'): were. treated. with-v 5 ml.;of:solutions.ofDowrCorningDc 200 Silicone fluid (viscosity "grade 350'. centistokes) in carbon:

percentto 0.001 percent. Treated plates were rubbed thoroughly with a clean soft. cloth. Amylose films were cast as in Example 1 (but without the dye)v on these treated plates and also on an untreated glass plate for comparison. Films were peeled only with difficulty from the untreated surface and from those-surfaces treatedwith 0.001 percent and 0.002 percent concentrations, while the films. cast on the plate treatedwith 1-5 percent solutions showed streakiness. Also, the solution tended to puddle. centration of 0.01 percent seemed to'promote consistently easyremoval of films without change in appearance or properties of the films.

.EXAMPLE3 An amylose solution was prepared as in Example 1, but no dyestufi was included, and a commercial mixture of isomeric amyl alcohols (Pentasol) was used instead of butanol. The Pentasol was removed by distillation prior to casting the film as in Example 1. The clear films, approximately 0.03 mm. in thickness, which were easily; removed from the silicone-treated plate, had a-dry tensile strength of 7.4 kg./mm. at 50 percent relative humidity and 72 F. They had a folding endurance of 579 Schopper double folds, a burst resistance (Muller) of 30.7 points, and a tear resistance of 4.7 g. determined by the Elmendorf machine.

EXAMPLE 4 EXAMPLE 5 Films were prepared from aqueous amylose solutions using ethanol to promote solubility of the amylose in water. A slurry of 20 g. corn amylose in70 ml. ethanol was poured into 200 ml. of water at 70C. which was being stirred rapidly. The ethanol was removed by distillation, and the water thus removed was replaced with fresh hot water. Films were cast as in Example 3 from the hot solution on silicone-treated plates. These films had properties similar. to those cited above, 0.03 mm. thick, a dry tensile strength of 8.0 kg./mm. underwent 890 Schopper double folds, a, burst resistance of 31 points (Muller), and a tear strength of 6 g. (Elmendorf).

EXAMPLE 6 Films were prepared from tapioca starch amylose by the procedure of Example 1, except that the dye was omittedand the plates siliconetreated. The amylose solution was considerably more viscous than a corresponding solution from corn amylose, and set somewhat slower to the gel stage. The resulting tapioca amylose films after drying were, however, practically identical in physical properties to those from corn amylose.

EXAMPLE 7 Films prepared as in Example 1 (dye omitted; plates silicone-treated) from white potato amylose were like those from tapioca amylose as described in Example 6.

A con- 6 EXAIVIPLEB An amylose solution prepared as inExamp1e1, omitting the dye, was cast into films onlchrome'i After" standing at room temperature for tenminute s,

surfaced silicone-treated metal plates.

one film was placed in a forced-draft oven main tained at -120 C. In 10-15 minutes the film' appeared dry and was removed from theoven; It was found to have fipercent haze and tensile strengths of 7.7 kg./mm. at 50 percent relative, humidity and 0.37 kg./mm. when completely wet. Another film, similarly cast and dried; showed 5 percent haze and tensile strengths of 78 and 0.40 kg./mm. (50 percent R. H. and wet,

respectively). Film prepared in the same way, except dried atroom temperature, normally has 10 percent haze, and tensile strength'sof 7.3 kg./mm. (5-0 percent R. H.) and 0.20 kg./mm.

(wet) r EXAMPLE 9 An amylose solution prepared as in Example "1, omitting the dye, was cast into films on chrome surfaced, silicone-treated metal plates at room temperature. One film, immediately on gelling, wa placed in an autoclave and treated with steam at 15 p. s. i. gage for 5 minutes followed bya stream of air, also at 15 p. s. i. gage-fore minutes. On removal from the autoclave, the film appeared nearly dry and soon was completely so, whereas, the other films had tobe left -overr Test results 1 night to dry at room temperature.

were:

Films made from certain special types 015 amylose may be much hazier than thoselobta ined; from corn amylose which has been prepared inl the ordinary way (see Schoch, J. A. C. S. 64,2957 (1942 Three samples of films from such'special amyloses, immediately after being cast on chrome plates and gelling, were autoclaved for15minutes in steam at 15 p. s. i.- gage, then cooled 15 minutes in a stream of air at the same pressure} The amylose of Sample 1 was from enzyme-modified and that of Sample 3 from acid-modifiedcorn starch, so that both were well below the usual Sample '2 represents a high molecular weight amylose prepared from corn,

molecular weight.

starch by a special procedure.

Table II ,1

Tensile [strength 5 Dn-ed at percent Dry Wet Room temperature 30 7. 3 0.08

sample 1 {gm C.tsteam t 5% 8.2 0. 24 0on1 empera ure. 16 6.9 0.20 Sample 2 20 0. steamflt e 8.2 0.43 com tempera ure 52 7. 5 0. 03

sample 3 0. steam 7 6.2 0.36

EXAMPLE 11 Ten grams of non-retrograded corn amylose was added slowly to 100 ml. of water at 82 C.

acosg'zas which was being stirredfvigorously in a beaker. This temperature. was maintained ,for 35 minutes during. which ..time awatch glass was kept. on .the beaker to "minimize evaporation and,

water was added to replace the amount so lost. This solution was .filtered through av heated frittedglass funnel. Alarge proportion of the original 10 g. wasnot dissolved and was removed in thefiltrationstep. Afilmcast from the,sol-

uble portion had '57 percent haze, less lustre than. films. previously described. in Examples 1-1(), .a,

dry tensile strength oi 7 .2 kgJmmF. at 72? F. and 50 percent R. H.,. and endured. 651 Schopper doublefoldsbefore breaking.

EXAMPLE 12 Five grams ,of non-retr'ogradedv corn amylose was added to 50 ml. of boiling Water which was being stirred in a round-bottomed flask. The mixture was refluxed for l hour with stirring. Solution was slow' with the result that some gelatinous amylosehardened on the bottom inner surfaceof the flasks (in some cases'it'is difiicultto-avoid scorching of this amylase). After filtration, films were'cast as in Example 3. The films had 165 percenthazea tensile strength of 618 kgn/mmfl, and a folding endurance of 529 Schopperdouble folds.

We claim:

' 1. The process comprising dissolving corn amylose in water containing a water soluble amylose compleXin-g agent taken from the class of lower alkanols, heating to obtain a clear solution, removing the complexing agent by distillation, leaving an aqueous corn amylose solution, forming said solution upon a surface at room temperature, and allowing it to gel and dry to a film.

2. The process of claim 1 in which the complexing agent is butanol.

3. The process of claim 1 in which the complexing agent is ethanol.

4. The process of claim 1 in which the complexing agent is an amylalcohol.

5. The process of. claim 1 in which the cast film.in agelled but not dry state is subjected to heat treatment at 80. to 150 C. for 5 to minutes.

.6. A. process for the preparation ,of amylose filmswhich comprises mixinganamylaceous substance comprising. at least 50 percent amylose with. an aqueous solution of anamylose complexing agenthaving appreciable solubility in water, removing theamylose complexing agent, leaving ana'q'ueous amylose solution, and subsequently disposing the solutionupon a casting surface and drying the formed film.

,7, A process for the preparation of amylose films which comprises forming an amylose complex from an amylaceous substance, which substance comprises at least 50 percent amylose, in an' aqueous medium by means of an amylose complexing agent having appreciable solubility in water, taken from the group consisting of lower alkanols and glycol ethers of lower alkanols, re-

moving 'theamylose. complexing agent from .the. amylose. solutionathus produced. and:subsequentlydisposing the aqueous solution upon a casting surface and d'ryingthe-formed film.

8. The process. which comprises adding an amylaceous substance comprising at least .550

percent amylose to an .aqueousmedium contain-- ing an amylose complexing agent having appreciable solubility in water and selected from the group consisting. of low molecular weight all? phatic alcohols, heating the mixture until S0111?" tion of the amylose occurs, removing the complexing agent, leaving an aqueoussoluticn of amylose, and disposing'the aqueous solutionupon a casting surface and drying-the formed film.

9. Process of claim 8 in which the complexing agent is butanol.

10. Processof claim 8 in which the complexing agent is ethanol.

11. Process of claim 6 in which the compl'exing agent is pyridine.

12. The method of claim 8 in which the cast film is subjected to a heat treatment at a term perature of to C. for 5 to 20 minutes.

13. The method of claim 8 in which the cast film is subjected to a heat treatment with steam at a temperature of 80 to 150 C. f0r'5'to 20 minutes.

14. The method of claim 8 in which the cast film is subjected to a heat treatment with air at a temperature of 80 to 150 C. for 5 to 20 minutes, said treatment taking place during the drying of the film.

15. The method of claim 8 in which the film is cast upon a surface treated with a silicone polymer.

16. The process comprising mixing an 'amyl-- REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,137,168 Levey Nov. 15, 1938 2,461,480 Rockmeyer Feb. 8, 1949 OTHER REFERENCES Ziegler: Plastics Technology, India Rubber World, September 1946, pp. 826-829. 

